Triphenylphosphine → HCID 57554465, compound

HRID 551992Notes

Reaction equation

HRID 551992 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([S:8]([N:11]([CH2:18][C:19]2[CH:20]=[CH:21][C:22]([F:29])=[C:23]([CH:28]=2)[C:24]([O:26][CH3:27])=[O:25])[CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH3:17])(=[O:10])=[O:9])=[CH:4][CH:3]=1.[CH2:30]([C:34]1[CH:39]=[CH:38][C:37]([C:40]#[CH:41])=[CH:36][CH:35]=1)[CH2:31][CH2:32][CH3:33].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>CN(C=O)C.CCOCC.[Pd](Cl)Cl.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Cu]I>[CH2:30]([C:34]1[CH:35]=[CH:36][C:37]([C:40]#[C:41][C:2]2[CH:3]=[CH:4][C:5]([S:8]([N:11]([CH2:18][C:19]3[CH:20]=[CH:21][C:22]([F:29])=[C:23]([CH:28]=3)[C:24]([O:26][CH3:27])=[O:25])[CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH3:17])(=[O:9])=[O:10])=[CH:6][CH:7]=2)=[CH:38][CH:39]=1)[CH2:31][CH2:32][CH3:33]

Participants

8

Reactant 3

HCID 11776TriphenylphosphineHCID 27751321-Butyl-4-ethynylbenzeneHCID 57554548HCID 57554548, compound

Product 1

HCID 57554465HCID 57554465, compoundYield 63.3%

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 6102075Dichlorobis(triphenylphosphine)palladiumCatalystHCID 3283Diethyl EtherSolventHCID 6228DimethylformamideSolvent

Conditions

Temperature
150 °C

Procedure

To a solution of methyl 5-{[[(4-bromophenyl)sulfonyl](hexyl)amino]methyl}-2-fluorobenzoate (96 mg; 0.20 mmol) in DMF (5 mL) were added (Aldrich, p-butylphenylacetylene (31 mg; 0.20 mmol), bis(triphenylphosphine) palladium (II) chloride (6.9 mg; 0.01 mmol), copper(I) iodide (1.9 mg; 0.01 mmol), triphenylphosphine (10.4 mg; 0.04 mmol) and TEA (0.08 mL; 0.59 mmol). The mixture was stirred for 1500 s at 150° C. under MW. The mixture was diluted with Et2O (50 mL) and the precipitate obtained filtrated off. Filtrate was washed with HCl 1N and with brine (75 mL). The organic layer was dried over magnesium sulfate and the solvent was removed under reduced pressure. Purification by flash chromatography using silicagel (c-Hex:EtOAc, 9:1 then 1:1) gave 66 mg (63.3%) of the title compound as a white solid. HPLC: Rt=6.12 min (purity=99.6%). LC/MS: M+(ESI): 564.4. 1H NMR (CDCl3) δ: 7.79 (d, J=8.3 Hz, 3H) 7.64 (d, J=8.7 Hz, 2H), 7.56 (m, 1H), 7.46 (d, J=8.3 Hz, 2H), 7.19 (d, J=7.9 Hz, 2H), 7.15 (s, 1H), 4.33 (s, 2H), 3.92 (s, 3H), 3.11 (t, J=7.5 Hz, 2H), 2.63 (t, J=7.7 Hz, 2H), 1.61 (t, J=7.7 Hz, 2H), 1.35 (m, 5H), 1.15 (m, 5H), 0.93 (t, J=7.3 Hz, 3H), 0.81 (t, J=6.9 Hz, 3H).

Workup

  1. customthe precipitate obtained
  2. filtrationfiltrated off
  3. washFiltrate was washed with HCl 1N and with brine (75 mL)
  4. dry with materialThe organic layer was dried over magnesium sulfate
  5. customthe solvent was removed under reduced pressure
  6. customPurification by flash chromatography

Sources & evidence

ORD record
ord-d106f3c26420492bb03c4b5c16f39863
Source dataset
uspto-grants-2011_05
Patent number
US07947851B2

Reaction notes

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